Branched chain saturated ketones, organoleptic uses thereof and process for preparing same

ABSTRACT

Described is the novel compound genus defined according to the structure: ##STR1## wherein R 1  is C 1  -C 3  lower alkyl useful in augmenting or enhancing the aroma or taste of consumable materials including perfumes, colognes, perfumed articles (including solid or liquid anionic, cationic, nonionic or zwitterionic detergents and perfumed polymers) smoking tobacco or smoking tobacco articles.

This is a divisional of application Ser. No. 399,067, filed July 16,1982 which, in turn, is a continuation-in-part of application for U.S.Letters Patent Ser. No. 354,389 filed on Mar. 2, 1982 which, in turn, isa divisional of application for U.S. Letters Patent Ser. No. 252,334filed on Apr. 9, 1981, now U.S. Pat. No. 4,336,164 issued on June 22,1982, which, in turn, is a continuation-in-part of application for U.S.Letters Patent Ser. No. 212,887 filed on Dec. 4, 1980, now U.S. Pat. No.4,318,934 issued on Mar. 9, 1982.

BACKGROUND OF THE INVENTION

Materials which can provide amber, woody and fruity aroma profiles withvetiver-like topnotes particularly those materials which are relativelyinexpensive are highly sought after in the art of perfumery. Many of thenatural materials which provide such fragrance profiles and contributedesired nuances to perfumery compositions and perfumed articlesubstances are high in cost, vary in quality from one batch to anotherand/or are generally subject to the usual variations of naturalproducts.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace the essential fragrance notes provided by naturalessential oils or compositions thereof. Unfortunately, many of thesesynthetic materials either have the desired nuances only to a relativelysmall degree or else contribute undesirable or unwanted odor to thecomposition. The search for materials which can provide a more refinedamber, woody, fruity and vetiver-like aroma has been difficult andrelatively costly in the areas of both natural products and syntheticproducts.

Materials which can provide woody, oriental and minty aroma and tasteprofiles both prior to and on smoking in the mainstream and thesidestream of smoking tobacco articles are desirable for augmenting orenhancing the aroma and taste of smoking tobacco and smoking tobaccoarticles, e.g. cigarettes and cigars.

Even more desirable is a product that can serve to substitute fordifficult-to-obtain natural perfumery oils and expensive syntheticingredients of perfume compositions and, at the same time, substitutefor expensive flavoring ingredients in smoking tobacco and in smokingtobacco articles.

None of the chemicals of the prior art which are ketones have aromaprofiles or chemical structures which are even remotely similar to thecompounds of my invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. AA represents the GLC profile for the reaction product of Example Ausing a 70% sulfuric acid catalyst at 35° C.

FIG. AB represents the GLC profile for the reaction product of Example Ausing the Amberlyst®15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of ExampleA, using an Amberlyst®15 catalyst at 100° C.

FIG. AD represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst and an alpha-methylstyrene diluent at35° C. according to the conditions of United Kingdom PatentSpecification No. 796,130 (crude reaction product).

FIG. AE represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst, at 35° C. and an alpha-methyl styrenediluent according to the conditions of United Kingdom PatentSpecification No. 796,130 (distilled reaction product) (boiling range36°-38° C. at 4-5 mm.Hg. pressure).

FIG. BA represents the NMR spectrum for Peak 1 of the GLC profile ofFIG. AE.

FIG. 2J represents the NMR spectrum for a mixture of compounds havingthe structures: ##STR2## produced according to Example 1.

FIG. BB represents the infra-red spectrum for Peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the NMR spectrum for Peak 2 of the GLC profile ofFIG. AE.

FIG. D represents the NMR spectrum for Peak 2 of the GLC profile of FIG.AB.

FIG. 1 sets forth the GLC profile for the reaction product of Example 1,containing compounds defined according to the structure: ##STR3##wherein in each molecule of the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines arecarbon-carbon single bonds.

FIG. 2A represent the infra-red spectrum for Peak 3 of the GLC profileof FIG. 1.

FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC profileof FIG. 1.

FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC profileof FIG. 1.

FIG. 2D represents the infra-red spectrum for Peak 6 of the GLC profileof FIG. 1.

FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC profileof FIG. 1.

FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC profileof FIG. 1.

FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC profileof FIG. 1.

FIG. 2J represents the NMR spectrum for a mixture of compounds havingthe structures: ##STR4## produced according to the Example I.

FIG. 2K represents the NMR spectrum for the compound having thestructure: ##STR5## produced according to Example I.

FIG. 2L represents the NMR spectrum for the compound containing thestructure: ##STR6## produced according to Example I.

FIG. 3 is the GLC profile for bulked fractions 10-16 of the distillationproduct of the reaction product of Example II containing the compounddefined according to the structure: ##STR7##

FIG. 4 is the NMR spectrum for bulked fraction 10-16 of the distillationproduct of the reaction product of Example II (solvent: CFCl₃ ; fieldstrength 100 MHz).

FIG. 5 is the infra-red spectrum for bulked fractions 10-16 of thedistillation product of the reaction product of Example II.

DISCLOSURES INCORPORATED BY REFERENCE HEREIN

The following application for U.S. Letters Patent and issued Patents areincorporated by reference herein:

(a) U.S. Application For Letters Patent, Ser. No. 160,788 filed on June19, 1980 now U.S. Pat. No. 4,287,084 issued on Sept. 1, 1981 (entitled:"Use of Mixture of Aliphatic C₁₀ Branched Olefins in Augmenting orEnhancing the Aroma of Perfumes and/or Perfumed Articles") setting forththe use of the compounds having the structures: ##STR8## or genericallythe compounds defined according to the structure: ##STR9## wherein R₁ ",R₂ ", R₃ ", R₄ " and R₅ " represents hydrogen or methyl with three of R₁", R₂ ", R₃ ", R_(4") and R₅ " representing methyl and the other two ofR₁ ", R₂ ", R₃ ", R₄ " and R₅ " representing hydrogen;

(b) Application for U.S. Letters Patent, Ser. No. 188,576 filed on Sept.18, 1980 now U.S. Pat. No. 4,303,555 issued on Dec. 1, 1981, acontinuation-in-part of Ser. No. 160,788 filed on June 19, 1980; and

(c) Application for U.S. Letters Patent, Ser. No. 184,132 filed on Sept.4, 1980 now U.S. Pat. No. 4,321,255 issued on Mar. 23, 1982, entitled"Branched Ketones, Organoleptic Uses Thereof and Process for PreparingSame" disclosing the reaction: ##STR10## wherein R₁ ', R₂ ' and R₃ 'represent C₁ -C₃ lower alkyl and R₄ ' is either of R₁ ', R₂ ' or R₃ 'and wherein X' is also chloro, or bromo, and the use of the resultingcompounds for their organoleptic properties.

The instant application is directed to the use of the compounds definedaccording to the generic structure: ##STR11## as starting materialswherein R₄ ' is C₁ -C₃ lower alkyl and wherein one of the dashed linesrepresents a carbon-carbon double bond and each of the other of thedashed lines represent carbon-carbon single bonds produced according tothe process of Application for United States Letters Patent, Ser. No.184,132 filed on Sept. 4, 1980 now U.S. Pat. No. 4,321,255 issued onMar. 23, 1982, entitled "Branched Ketones, Organoleptic Uses Thereof andProcess for Preparing Same."

THE INVENTION

It has now been determined that certain branched chain saturated ketonesare capable of imparting a variety of flavors and fragrances to variousconsumable materials. Briefly, our invention contemplates branched chainsaturated ketones defined according to the generic structure: ##STR12##wherein R₁ is C₁ -C₃.

The branched chain saturated ketones of my invention are either usablein admixture with one another, or the isomers are usable in admixturewith one another such as mixtures of the stereoisomers defined accordingto the structures: ##STR13##

Insofar as the hydrogenation reaction is concerned with the ketonehaving the structure: ##STR14## as the starting material or one of theketones defined according to the structure: ##STR15## as being astarting material, the ketone is reacted with hydrogen in the presenceof a Raney nickel catalyst or a palladium on carbon catalyst or a"Lindlar" catalyst (palladium on calcium carbonate) or palladium onbarium sulfate. The percentage of palladium in the palladium on carboncatalyst or in the palladium on calcium carbonate catalyst or in thepallaidum on barium sulfate catalyst varies from about 2% up to about 7%with a percentage of palladium in the palladium on carbon catalyst or inthe palladium on calcium carbonate catalyst or in the palladium onbarium sulfate catalyst being preferred to be 5%. The temperature ofreaction for the hydrogenation may vary from about 130° up to about 250°C. with a preferred reaction temperature of 150° to 180° C. The pressureof hydrogen over the reaction mass may vary from about 50 psig to about200 psig with the most preferred pressure being 50 to 80 psig. It ispreferred in order to form the product having the structure: ##STR16##that the reaction be carried out in the absence of a solvent.

When a palladium containing catalyst is used, the percentage of catalystin the reaction mass may vary from 0.125% up to about 2.0% with apercentage of catalyst of about 0.25% being preferred. When a Raneynickel catalyst is used the percentage of catalyst in the reaction massmay vary from about 3% up to about 10% with a percentage of catalyst ofabout 5% being preferred.

In general the reaction is illustrated thusly: ##STR17## wherein R₁represents C₁ -C₃ alkyl.

The individual branched chain saturated ketones of my invention can beobtained in purer form or in substantially pure form by conventionalpurification techniques. Thus, the products can be purified bydistillation, extraction, crystallization, preparative chromatographictechniques (including high pressure liquid chromatography) and the like.It has been found desirable to purify the branched chain unsaturatedsecondary alcohols of our invention by fractional distillation undervacuum.

It will be appreciated from the present disclosure that the branchedchain saturated ketones and mixtures thereof according to the presentinvention can be used to alter, vary, fortify, modify, enhance orotherwise improve the flavor and aroma of a wide variety of materialswhich are ingested, consumed or otherwise organoleptically sensed,particularly including perfume compositions, perfumed articles andsmoking tobacco compositions and smoking tobacco articles.

The term "alter" in its various forms will be understood herein to meanthe supplying or imparting of a flavor character or note or aromacharacter to an otherwise bland, relatively aromaless or tastelesssubstance, or augmenting an existing flavor or aroma characteristicwhere the natural flavor or aroma is deficient in some regard orsupplementing the existing flavor or aroma impression to modify theorganoleptic character.

The term "enhance" is intended herein to mean the intensification of aparticular aroma or taste nuance (particularly in perfumes, perfumedarticles or smoking tobaccos) without the changing of the quality ofsaid nuance and without adding an additional aroma or taste nuance tothe consumable material, the organoleptic properties of which areenhanced.

The term "tobacco" will be understood herein to mean a natural productsuch as, for example, burley, Turkish tobacco, Maryland tobacco,flue-cured tobacco and the like including tobacco-like or tobacco-basedproducts such as reconstitued or homogenized leaf and the like, as wellas tobacco substitutes intended to replace natural tobacco, such aslettuce and cabbage leaves and the like. The tobaccos and tobaccoproducts in which the branched chain saturated ketones of my inventionand useful include those designed or used for smoking such as incigarette, cigar and pipe tobacco, as well as products such as snuff,chewing tobacco and the like.

The branched chain saturated ketones of my invention can be used tocontribute warm, vetiver-like, woody, fruity and amber aromas. Asolfactory agents the branched chain unsaturated secondary alcohols ofthis invention can be formulated into or used as components of a"perfume composition".

The term "perfume composition" is used herein to mean a mixture oforganic compounds, including, for example, alcohols, other than thealcohols of this invention, aldehydes, ketones, nitriles, esters, andfrequently hydrocarbons which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain: (a) the main note of the "bouquet"or foundation-stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lead a particular note to the perfume throughout allstages of evaporation, and substances which retard evaporation; and (d)topnotes which are usually low-boiling fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of branched chain saturated ketones of this invention whichwill be effective in perfume compositions depends on may factors,including the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.05% and as much as 5% of the branched chain saturatedketones of this invention can be used to impart, augment or enhancewarm, intense, amber, woody, fruity and vetiver aroma profiles to soaps,cosmetics, solid or liquid anionic, cationic, nonionic and zwitterionicdetergents and other products. The amount employed can range up to 50%of the fragrance and can be as low as 1% of the original fragrance andwill depend on considerations of cost, nature of the end product, theeffect desired in the finished product and the particular fragrancesought.

The branched chain saturated ketones of this invention can be used aloneor in a perfume composition as an olfactory component in detergents, andsoaps, space odorants and deodorants, perfumes, colognes, toilet waters,bath salts, hair preparations such as lacquers, brilliantines, pomades,and shampoos, cosmetic preparations such as creams, deodorants, handlotions and sun screens, powders such as talcs, dusting powders, facepowder, and the like. When used as an olfactory component of a perfumedarticle, as little as 0.05% of one or more of the branched chainsaturated ketones will suffice to impart warm, vetiver, woody, amber andfruity aroma nuances. Generally no more than 5.0% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the branched chain saturated ketones taken alone or taken togetherwith other ingredients. The vehicle can be a liquid such as an alcoholsuch as ethanol, a glycol such as propylene glycol, or the like. Thecarrier can be an absorbent solid such as a gum or a microporous polymeror components for encapsulating the composition such as by means ofcoacervation.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco products and additives therefor, as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired oriental and woody flavor andaroma characteristics are created or enhanced and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable woody, oriental flavor and aromacharacteristics may be imparted to smoking tobacco products and may bereadily varied and controlled to produce the desired uniform flavoringcharacteristics prior to and on smoking in the mainstream and in thesidestream.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone of the secondary alcohols of my invention.

In addition to the one or more secondary alcohols of my invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in admixture withthe secondary alcohols as follows:

I. Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Beta-Damascone;

1-[3-(methylthio)butyrol[2,3,3-trimethyl-cyclohexene;

Beta-Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl acetate;

2-Hexenol-1;

2-methyl-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2-1-b)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971.

II. Natural Oils:

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more of thebranched chain saturated ketones of my invention or more of the aboveindicated additional flavoring additives may be added to the smokingtobacco material, to the filter or to the leaf or paper wrapper. Thesmoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as the augmentation, or the enhancement or the imparting of thewoody, oriental and minty notes are concerned, we have found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of saturated ketons of my invention is between 250 ppm and 1,500ppm (0.025%-1.5%) of the active ingredients to the smoking tobaccomaterial. I have further found that satisfactory results are obtained ifthe proportion by weight of the sum total of saturated ketones used toflavoring material is between 2,500 and 10,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the secondary alcohols in thetobacco product may be employed. Thus, the secondary alcohols takenalong or along with other flavoring additives may be dissolved in asuitable solvent such as ethanol, n-pentane, diethyl ether and/or othervolatile organic solvents and the resulting solution may either besprayed on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of one or more saturated ketones of this invention takenalone or further together with other flavoring additives as said forthabove may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product, or itmay be applied to the filter by either spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or more of thesaturated ketones of this invention in excess of the amounts orconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

In accordance with one specific example of my invention, an aged, curedand shredded domestic burley tobacco is spread with a 20% ethyl alcoholsolution of a mixture of compounds having the structure: ##STR18##produced according to Example V, infra, in an amount to provide atobacco composition containing 800 ppm by weight of the secondaryalcohol mixture on a dry basis. Thereafter, the ethyl alcohol is removedby evaporation and the tobacco is manufactured into cigarettes by theusual techniques. The cigarette when treated as indicated has a desiredand pleasing aroma which is detectable in the main and side streams whenthe cigarette is smoked. This aroma is described as being sweet,oriental-like, woody and Turkish tobacco-like nuances.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the saturated ketones of my invention can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, the saturated ketonesof this invention can be added to certain tobacco substitutes of naturalor synthetic origin (e.g. dried lettuce leaves) and, accordingly, byterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

The following examples A-I are given to illustrate techniques forproducing the precursors for the compounds of my invention as it ispresently preferred to practice it. Example II and onwards are given toillustrate embodiments of my invention as it is presently preferred topractice it. It will be understood that these examples are illustrativeand the invention is not to be considered restricted thereot except asindicated in the appended claims.

EXAMPLE A Preparation of Di-isoamylene Derivatives

Reaction: ##STR19## (wherein in each of the molecules indicated, one ofthe dashed lines is a carbon-carbon double bond and the other of thedashed lines are carbon-carbon single bonds).

Di-isoamylene is prepared according to one of the procedures set forthin the following references:

i--Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3, 1975p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in Sulfuric andSulfuric-Phosphoric Acid Mixtures).

ii--Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p.281 (Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-hexene and3,5,5-Trimethyl-2-heptene in Relation to the Dimerization ofIsoamylenes)

The resulting material was distilled in a fractionation column in orderto separate the di-isoamylene from the higher molecular weight polymers,which are formed during the reaction as by-products.

FIG. AA represents the GLC profile for the reaction product of Example Ausing a 70% sulfuric acid catalyst at 35%C.

FIG. AB represents the GLC profile for the reaction product of Example Ausing an Amberlyst®15 acidic ion exchange resin catalyst at atemperature of 150° C.

FIG. AC represents the GLC profile for the reaction product of ExampleA, using an Amberlyst®15 catalyst at 100° C.

FIG. AD represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst and an alpha-methylstyrene diluent at35° C. according to the conditions of United Kingdom PatentSpecification No. 796,130 (crude reaction product).

FIG. AE represents the GLC profile for the reaction product of ExampleA, using a sulfuric acid catalyst, at 35° C. and an alpha-methyl styrenediluent according to the conditions of United Kingdom PatentSpecification No. 796,130 (distilled reaction product) further (boilingrange 36°-38° C. at 4-5 mm.Hg. pressure).

FIG. BA represents the NMR spectrum for Peak of the GLC profile of FIG.AE.

FIG. BB represents the infra-red spectrum for Peak 1 of the GLC profileof FIG. AE.

FIG. CA represents the NMR spectrum for Peak 2 of the GLC profile ofFIG. AE.

FIG. CB represents the infra-red spectrum for Peak 2 of the GLC profileof FIG. AE.

FIG. D represents the NMR spectrum for Peak 2 of the GLC profile of FIG.AB.

EXAMPLE I Preparation of Acetyl Derivative of Diisoamylene

Reaction: ##STR20## wherein in each of the structures containing dashedlines, these structures represent mixtures of molecules wherein in eachof the molecules, one of the dashed lines respresents a carbon-carbondouble bond and each of the other of the dashed lines respresentcarbon-carbon single bonds.

Into a 2-liter reaction flask equipped with stirrer, thermometer, reflexcondenser and heating mantle, is placed 1000 g of acetic anhydride and80 g of boron trifluoride diethyl etherate. The resulting mixture isheated to 80° C. and, over a period of 40 minutes, 690 g of diisoamyleneprepared according to the illustration in Example A, supra is added. Thereaction mass is maintained at 82°-85° C. for a period of 5.5 hours,whereupon it is cooled to room temperature. The reaction mass is thenadded to one liter of water and the resulting mixture is stirred therebyyielding two phases; an organic phase and an aqueous phase. The organicphase is separated from the aqueous phase and neutralized with twoliters of 12.5% sodium hydroxide followed by one liter of saturatedsodium chloride solution. The resulting organic phase is then dried overanhydrous sodium sulfate and distilled in a one plate distillationcolumn, yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     mm/Hg  Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (g.)                                       ______________________________________                                        1         33/68   62/77     8/8    161                                        2         69      79        4      100                                        3         72      86        3.0    191                                        4         88      134       3.0    189                                        ______________________________________                                    

The resulting material is then distilled on a multi-plate fractionationcolumn, yielding the following fractions at the following reflux ratios:

    ______________________________________                                                Vapor   Liquid          Reflux Weight of                              Fraction                                                                              Temp.   Temp.    mm/Hg  Ratio  Fraction                               No.     (°C.)                                                                          (°C.)                                                                           Pressure                                                                             R/D    (g.)                                   ______________________________________                                        1       30/65   62/83    5/5    9:1    30.8                                   2       68      84       5      9:1    52.8                                   3       68      85       5      9:1    34                                     4       69      87       5      9:1    43                                     5       69      87       5      9:1    34                                     6       71      88       4      4:1    41                                     7       70      88       5      4:1    36.5                                   8       71      91       5      4:1    42                                     9       73      95       3      4:1    42.5                                   10      80      106      3      4:1    39                                     11      80      142      3      4:1    50.8                                   12      80      220      3      4:1    24                                     ______________________________________                                    

fractions 2-9 are bulked.

GLC, NMR, IR and mass spectral analyses yield the information that theresulting bulked fractions is a mixture of cis and trans isomers havinga generic structure: ##STR21## wherein in each of the molecules, one ofthe dashed lines is a carbon-carbon double bond and the other of thedashed lines is a carbon-carbon single bond and, primarily, this mixturecontains the molecular species (cis and trans isomers) as follows:##STR22##

FIG. 1 sets forth the GLC profile for the reaction product of Example I,containing compounds defined according to the structure: ##STR23##wherein in each molecule of the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines arecarbon-carbon single bonds.

FIG. 2A represents the infra-red spectrum of Peak 3 of the GLC profileof FIG. 1.

FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC profileof FIG. 1.

FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC profileof FIG. 1.

FIG. 2D represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC profileof FIG. 1.

FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC profileof FIG. 1.

FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC profileof FIG. 1.

FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC profileof FIG. 1.

FIG. 2K represents the NMR spectrum for the compound having thestructure: ##STR24## produced according to Example I.

FIG. 2L represents the NMR spectrum for the compound containing thestructure: ##STR25## produced according to Example I.

EXAMPLE II Preparation of Saturated Ketone

Reaction: ##STR26##

Into a 1 liter autoclave equipped for pressures up to 1000 psig isplaced 498 g of a mixture of compounds defined according to thestructure: ##STR27## (wherein in the mixture in each of the moleculesone of the dashed lines represents a carbon-carbon double bond and eachof the other of the dashed lines represent single bonds, producedaccording to Example I, bulked distillation fraction 2-9) and 2.5 g of5% Palladium on carbon. The reaction mass is pressurized with hydrogento a pressure in the range of 40-60 psig and the temperature of 165° C.and maintained at that temperature and pressure for a period of 4 hours.The autoclave is then cooled and opened and the reaction mass isfiltered yielding 475.1 grams of product. The product is thenfractionally distilled on a 14 inch vigreux column, yielding thefollowing fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm. Hg.                                                                              of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         66/82   105/90    14/14  8.4                                        2         85      94        14     8.1                                        3         87      95        14     7.3                                        4         88      95        --     8.5                                        5         88      95        --     12.0                                       6         88      95        --     10.7                                       7         89      95        14     18.1                                       8         89      95        14     19.4                                       9         89      95        14     19.5                                       10        89      95        14     31.8                                       11        89      95        14     29.6                                       12        89      95        14     47.7                                       13        90      95        14     45.3                                       14        90      95        14     47.7                                       15        90      98        14     41.0                                       16        91      98        14     43.6                                       17        92      99        14     13.4                                       18        92      101       14     19.8                                       19        92      103       14     17.7                                       20        94      110       14     9.0                                        21        90      150       14     5.8                                        22        89      230       14     3.6                                        ______________________________________                                    

FIG. 3 is the GLC profile for bulked fractions 10-16 of the foregoingdistillation (conditions: 10"×1/4 inch, 10% carbo x, programmed at80°-225° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for bulked fractions 10-16 of the foregoingdistillation (solvent: CFCl₃ ; field strength 100 MHz).

FIG. 5 is the infra-red spectrum for bulked fractions 10-16 of theforegoing distillation.

EXAMPLE III Perfume Formulation

The following vetiver perfume formulation is prepared:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Vetivone         25                                                           Saturated Ketone                                                              having the structure:                                                          ##STR28##                                                                    (Produced according to                                                                         25                                                           Example II, bulked                                                            fractions 10-16)                                                              Vetiverol        5                                                            Musk ketone      8                                                            Styrax essence   4.5                                                          ______________________________________                                    

The addition of the saturated ketone having the structure: ##STR29##prepared according to Example III imparts to this vetiver formulation anintense woody, fruity and amber nuances.

EXAMPLE IV Perfumed Liquid Detergent

Concentrated liquid detergents with aromas as described in Table I below(which detergents are produced from the lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818issued on Apr. 6, 1976) are prepared containing one of the substancesset forth in Table I below. They are prepared by adding andhomogeneously mixing the appropriate quantity of substance as indicatedin Table I below. The detergents all possess aroma profiles as set forthin Table I below, the intensity increasing with greater concentrationsof the composition of matter as set forth in Table I below:

                  TABLE I                                                         ______________________________________                                        Aroma Ingredient Aroma Profile                                                ______________________________________                                        Saturated ketone having                                                                        Anintense woody, amber and                                   the structure:   fruity aroma profile.                                         ##STR30##                                                                    produced according to                                                         Example III, bulked                                                           fractions 10-16.                                                              Perfume composition                                                                            A vetiver aroma with intense                                 of Example III.  woody, amber and fruity under-                                                tones.                                                       ______________________________________                                    

EXAMPLE V Preparation of a Soap Composition

One hundred grams of soap chips (IVORY®) manufactured by the Procter &Gamble Company of Cincinnati, Ohio, are melted and intimately admixedwith one of the aroma materials as set forth in Table I of Example IVsupra, the amount of composition of matter of Table I of Example IVbeing one gram of each composition of matter. The conditions of mixingare: 180° C., 3 hours, 12 atmospheres pressure. At the end of the mixingcycle, while the soap is still under 12 atmospheres pressure, themixture of soap and perfume ingredient is cooled to room temperature. Atthis temperature, the resulting mixture is in a solid state. Theresulting soap block is then cut up into soap cakes. Each of the soapcakes manifests an excellent aroma as set forth in Table I of ExampleIV. None of the soap samples show any discoloration even after two weeksin the oven at 90° F.

EXAMPLE VI Preparation of a Detergent Composition

A total of 100 grams of a detergent powder (nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of one of the compositions of matter as set forth in Table I ofExample IV until a substantially homogeneous composition is obtained.Each of the compositions has excellent aroma profiles as set forth inTable I of Example IV.

EXAMPLE VII Perfumed Liquid Detergents

Concentrated liquid detergents with rich, pleasant aromas as set forthin Table I of Example IV are prepared containing 0.10%, 0.15% and 0.20%of each of the compositions of matter set forth in Table I of ExampleIV. They are prepared by adding and homogeneously admixing theappropriate quantity of composition of matter of Table I of Example IVin the liquid detergent. The liquid detergents are all produced usinganionic detergents containing a 50:50 mixture of sodium lauroylsarcosinate and potassium N-methyl lauroyl tauride. The detergents allpossess pleasant aromas as defined in Table I of Example IV, theintensity increasing with greater concentrations of composition ofmatter of Table I of Example IV.

EXAMPLE VIII Tobacco Formulation

A tobacco mixture is prepared by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. One-half of the cigarettes are then treated with 500 or1000 ppm of the saturated ketone defined according to the structure:##STR31## The other half of the cigarettes are "control cigarettes" anddo not contain any of the saturated ketone of Example II but onlycontain untreated flavor formulation as set forth above. The controlcigarettes and the treated experimental cigarettes are then evaluated bypaired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be, onsmoking, more Turkish tobacco-like, more aromatic and to have sweet,woody/oriental and fruity aroma nuances in both the main stream and theside stream.

What is claimed is:
 1. At least one compound defined according to thestructure: ##STR32## wherein R₁ is C₁ -C₃ lower alkyl.
 2. The compoundof claim 1 wherein R₁ is methyl.
 3. A composition of matter consistingessentially of at least one compound defined according to the structure:##STR33## wherein R₁ is C₁ -C₃ lower alkyl produced according to aprocess consisting essentially of the step of contacting with hydrogenat least one compound defined according to the structure: ##STR34##wherein R₁ is C₁ -C₃ lower alkyl and one of the dashed lines representsa carbon-carbon double bond and each of the other of the dashed linesrepresents carbon-carbon single bonds in the presence of a catalyst at atemperature in the range of 100°-200° C. and at a pressure in the rangeof from 40-400 psig.
 4. The product of claim 3 wherein in the processthe catalyst is palladium supported on carbon.
 5. The product of claim 3wherein R₁ is methyl.